JP2009226277A - Acetylene occluding material and manufacturing method, as well as high-purity acetylene supply device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a metallic complex which can store a large quantity of acetylene gas at so low a pressure as not causing cracking explosion. <P>SOLUTION: This acetylene occluding material composed of a porous metal complex, is configured to comprise a divalent transition-metal cation, a first ligand i.e. a divalent anion with a site capable of coordinated linkage to a metal and a second ligand with a site capable of coordinated linkage to a metal at its both ends. Thus, the acetylene occluding material comes to have pores suitable for adsorbing acetylene. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an acetylene storage material for safely storing acetylene, a method for producing the same, an acetylene storage container using the storage material, an acetylene supply device using the storage material, and an acetylene using the storage material. The present invention relates to a purification apparatus.

Conventionally, as a gas storage device containing acetylene, an organic configuration capable of bidentate coordination having a divalent metal ion and a nitrogen atom capable of coordinating to the divalent metal ion at a rigid skeleton utilization terminal. Organometallic complex composed of a ligand and 2,3-pyrazinedicarboxylic acid (Patent Document 1), a divalent metal ion, and an organic compound capable of bidentate arrangement having an atom capable of coordinating to the metal ion Chemical formula consisting of ligand and 2,3 pyrazinedicarboxylic acid (pyzdc): Cu ₂ (Ligand) (pyzdc) ₂
An organometallic complex having a three-dimensional structure represented by (Patent Document 2) and the like are known.
Japanese Patent No. 3746321 JP 2000-210559 A

  In the conventional organometallic complex, there is a space in the crystal structure, and the gas component is adsorbed and stored according to the size of the space and the characteristics of the constituent components. However, in the conventional metal complex described above, The problem was that a sufficient amount of acetylene gas could not be secured.

  The present invention has been made paying attention to such points, and an object thereof is to provide a metal complex capable of storing a large amount of acetylene gas at a low pressure that does not cause decomposition and explosion.

  In order to achieve the above-mentioned object, in the invention according to claim 1, a divalent transition metal cation and a first ligand which is a divalent anion having a site capable of coordinating with a metal, And having a pore suitable for acetylene adsorption composed of a second ligand having a site capable of coordinating and binding to a metal at both ends. Further, the invention according to claim 2 is directed to a divalent transition metal cation, a first ligand that is a divalent anion having a site capable of coordinating with a metal, and a metal at both ends. It is characterized by being composed of a second ligand having a site capable of positional bonding and having no charge.

  Furthermore, in the invention according to claim 5, a layered structure formed by a divalent transition metal cation and a first ligand that is a divalent anion having a site capable of coordinating with a metal, A porous structure is formed by connecting the second ligand in a columnar shape, and the pore diameter is controlled by a substituent introduced into the first ligand.

  In the present invention, a divalent transition metal cation, a first ligand that is a divalent anion having a site capable of coordinating with a metal, and a site capable of coordinating with a metal at both ends are provided. Since the second ligand constitutes pores suitable for acetylene adsorption, a large amount of acetylene gas can be stored at a low pressure that does not cause decomposition explosion.

  A cupric salt such as copper chloride or copper nitrate is used as a divalent transition metal cation, and a divalent anion having a site capable of coordinating with a metal is used as a first ligand, 2, 3 -Using pyrazinedicarboxylic acid, 4-aminomethylpyridine (4-amp) which is a substance having an asymmetric structure is used as a second ligand having no site that can be coordinated to a metal at both ends and having no electrification As a result, a porous metal complex having both a higher storage capacity and a pressure characteristic suitable for storage / release can be obtained.

  In addition, as a 2nd ligand which does not have this electrification, it changes into the above-mentioned 4-aminomethylpyridine (4-amp), 4- (2-aminoethyl) pyridine, 4- (3-aminopropyl) pyridine. The number of carbon chains to which an amino group is bonded may be increased to two or more.

In the procedure for synthesizing the porous metal complex described above, first, each raw material is weighed so as to have the following molar ratio.

Next, 2,3-pyrazinedicarboxylic acid (H ₂ pzdc), which is the first ligand, is dissolved in water in a container, and sodium bicarbonate is added to neutralize 2,3-pyrazinedicarboxylic acid. The secondary ligand 4-aminomethylpyridine (4-amp) is added to the neutralized solution and stirred and mixed.

  An aqueous copper nitrate solution is gradually added dropwise to the ligand solution. By dropping the aqueous copper nitrate solution, a powdery precipitate starts to form. Stirring is continued for a while after the dropping is completed. The precipitate is collected by suction filtration. At this time, the precipitate is washed with water and alcohol (methanol or ethanol) while sucking and then air-dried to measure the yield.

  At this time, the divalent transition metal salt includes a divalent cation of the first to third series transition metal elements, and includes a chemical species that does not have a bidentate or more chelate coordination to the metal as a counter ion. More specifically, chloride ions, nitrate ions, perchlorate ions, and the like are preferable.

  When the ligand is an acidic substance, it is neutralized by adding a base before mixing with other raw materials, and then adding a base. It is desirable that the neutralized solution does not contain impurities that may form a strong coordinate bond with the metal or the first and second ligands and prevent the formation of the target porous complex. From this point, it is most desirable to use an alkali metal hydroxide or carbonate (sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, etc.) as a base during neutralization. Further, the neutralized salt may be crystallized for isolation and purification.

  Furthermore, as a solvent, not only water but a polar organic solvent that is completely mixed with water (polar solvents such as alcohols such as methanol and ethanol, acetone, N, N′-dimethylformaldehyde, dimethyl sulfoxide, and 1,4-dioxane) Alternatively, a solvent prepared by mixing them in advance may be appropriately used depending on the solubility of each raw material. The organic solvent that separates water phase causes undesirable side reactions because the raw materials are not uniformly mixed.

  And as an order of mixing, it is appropriate to prepare a solution in which the first ligand and the second ligand are mixed in advance and to react this mixed solution with the metal salt. Mixing of a single ligand and a metal salt should be avoided because the desired product cannot be obtained depending on the combination thereof.

(1) 0.297 g (1.8 mmol) of 2,3-pyrazinedicarboxylic acid was dissolved in 100 mL of water as a first ligand in an Erlenmeyer flask to obtain a light brown aqueous solution.
(2) 0.296 g (3.5 mmol) of sodium bicarbonate was added to the solution to neutralize 2,3-pyrazinedicarboxylic acid. The neutralization was confirmed by visually observing the foaming of carbon dioxide.
(3) To the neutralized solution, 0.100 g (0.9 mmol) of 4-aminomethylpyridine was added and dissolved as the second ligand.
(4) While stirring the mixed solution of the ligand, a small amount of a pale blue aqueous solution obtained by dissolving 0.405 g (1.7 mmol) of copper nitrate trihydrate as a cupric salt in 100 mL of water. It was dripped one by one. When dropping was continued, a blue powdery precipitate was formed. Stirring was continued for about 1 hour after the completion of dropping.
(5) The product was subjected to suction filtration with a Buchner funnel to separate the solid and liquid, and the precipitate was collected. In order to remove unreacted substances, the precipitate was washed by pouring water and alcohol (methanol or ethanol) while continuing suction. This was air-dried to obtain a target complex.
(6) When acetylene adsorption was measured at 25 ° C., an adsorption amount of 67 mL per 1 g of complex was obtained near atmospheric pressure.

As a result of conducting elemental analysis and thermogravimetric analysis on the complex obtained in Example 1, the composition of the obtained complex has a metal to ligand ratio of Cu: pzdc (first Ligand): 4-amp (secondary ligand) is 1: 1: 0.5 (= 2: 2: 1) and agrees well with the value calculated assuming that two molecules of water are taken up per Cu atom. did.

  The results of thermogravimetric analysis are shown in FIG. From FIG. 1, a weight loss of about 11.5% was shown up to 100 ° C., and this value was in good agreement with the value (11.3%) that two molecules of water were adsorbed by elemental analysis.

[Comparative Example 1]
(1) 0.375 g (2.27 mmol) of 2,3-pyrazinedicarboxylic acid as a first ligand in an Erlenmeyer flask was dissolved in 100 mL of water to obtain a light brown aqueous solution.
(2) 0.296 g (3.5 mmol) of sodium bicarbonate was added to the solution to neutralize 2,3-pyrazinedicarboxylic acid. The neutralization was confirmed by visually observing the foaming of carbon dioxide.
(3) 0.1100 g (0.9 mmol) of pyrazine was added as a second ligand to the neutralized solution and dissolved.
(4) While stirring the mixed solution of the ligand, a small amount of a pale blue aqueous solution obtained by dissolving 0.405 g (1.7 mmol) of copper nitrate trihydrate as a cupric salt in 100 mL of water. It was dripped one by one. When dropping was continued, a blue powdery precipitate was formed. Stirring was continued for about 1 hour after the completion of dropping.
(5) The product was subjected to suction filtration with a Buchner funnel to separate the solid and liquid, and the precipitate was collected. In order to remove unreacted substances, the precipitate was washed by pouring water and alcohol (methanol or ethanol) while continuing suction. This was air-dried to obtain a target complex.
(6) When the acetylene adsorption amount was measured at 25 ° C., an adsorption amount of 42 mL per 1 g of the complex was obtained near atmospheric pressure.

[Comparative Example 2]
(1) 0.468 g (2.8 mmol) of 2,3-pyrazinedicarboxylic acid was dissolved in 50 mL of water as a first ligand in an Erlenmeyer flask to obtain a light brown aqueous solution.
(2) To the solution, 0.0470 g (5.6 mmol) of sodium bicarbonate was added to neutralize 2,3-pyrazinedicarboxylic acid. The neutralization was confirmed by visually observing the foaming of carbon dioxide.
(3) A solution obtained by dissolving 0.217 g (1.4 mmol) of 4,4′-bipyridyl in 50 mL of ethanol as the second ligand was added to the neutralized solution and mixed.
(4) While stirring the mixed solution of the ligand, a small amount of a pale blue aqueous solution obtained by dissolving 0.683 g (2.8 mmol) of copper nitrate trihydrate as a cupric salt in 100 mL of water. It was dripped one by one. When dropping was continued, a blue powdery precipitate was formed. Stirring was continued for about 1 hour after the completion of dropping.
(5) The product was subjected to suction filtration with a Buchner funnel to separate the solid and liquid, and the precipitate was collected. In order to remove unreacted substances, the precipitate was washed by pouring water and alcohol (methanol or ethanol) while continuing suction. This was air-dried to obtain a target complex.
(6) When the acetylene adsorption amount was measured at 25 ° C., an adsorption amount of 58 mL per 1 g of the complex was obtained near atmospheric pressure.

[Comparative Example 3]
Using the same raw material as in Example 1, the molar ratio of Cu: pzdc (first ligand): 4-amp (second ligand) is 1: 1: 2 so that the second ligand is excessive. The synthesis was performed in the same manner under the conditions of 2.
(1) 0.491 g (2.9 mmol) of 2,3-pyrazinedicarboxylic acid was dissolved in 100 mL of water as a first ligand in an Erlenmeyer flask to obtain a light brown aqueous solution.
(2) 0.492 g (5.9 mmol) of sodium bicarbonate was added to the solution to neutralize 2,3-pyrazinedicarboxylic acid. The neutralization was confirmed by visually observing the foaming of carbon dioxide.
(3) To the solution after neutralization, 0.631 g (5.8 mmol) of 4-aminomethylpyridine was added and dissolved as the second ligand.
(4) While stirring the mixed solution of the ligand, 0.703 g (2.9 mmol) of a pale blue aqueous solution of copper nitrate trihydrate was added dropwise as a cupric salt. When dropping was continued, a blue powdery precipitate was formed. Stirring was continued for about 1 hour after the completion of dropping.
(5) The product was subjected to suction filtration with a Buchner funnel to separate the solid and liquid, and the precipitate was collected. In order to remove unreacted substances, the precipitate was washed by pouring water and alcohol (methanol or ethanol) while continuing suction. This was air-dried and the yield was measured to be 0.861 g.
(6) When this product was heated to 130 ° C. under vacuum, it turned brown and was confirmed to be unstable.

  Thereby, even if the same raw material was used, it was confirmed that a product different from that in Example 1 was obtained when the second ligand was in an excessive amount. This product was decomposed during heating vacuum deaeration for removing adsorbed moisture and the like, and was unsuitable for use as a gas adsorbent.

この表からも分かるように、実施例１で示す本発明の錯体は、従来技術として例示した比較例１及び２で得られる錯体に比して、１５〜５９％のアセチレン吸着量の向上が見られる。 The measurement results of the acetylene adsorption amount at 25 ° C. and near atmospheric pressure in the complexes of Example 1 and Comparative Examples 1 and 2 are shown in the following table.

As can be seen from this table, the complex of the present invention shown in Example 1 shows 15 to 59% improvement in acetylene adsorption compared to the complexes obtained in Comparative Examples 1 and 2 exemplified as the prior art. It is done.

  Moreover, the relationship between the pressure of each complex and the amount of adsorption was as shown in FIG.

Furthermore, as a method for evaluating physical properties such as the surface area, pore volume, and pore diameter of the porous material, the complex of the present invention shown in Example 1 and the complex obtained in Comparative Example 1 exemplified as the prior art are generally used. The results of measuring the amount of nitrogen gas adsorbed at the liquefied nitrogen temperature are shown in FIG.
The complex obtained by the method of Comparative Example 1 has an adsorption isotherm that suddenly rises from a very low pressure, and exhibits a behavior characteristic of a porous material having pores called micropores having a diameter of 2 nm or less. On the other hand, the complex obtained by the method of the present invention (Example 1) showed a gentle curve with no rise in the low-pressure part. This isotherm is a characteristic behavior when it is non-porous. The increase in the amount of adsorption at a relative pressure of 0.8 is due to the liquefaction of nitrogen on the solid surface.
From these, it was confirmed that the complex obtained by the method of the present invention (Example 1) has a high affinity for acetylene and has pores that selectively adsorb acetylene molecules.

  Furthermore, as shown in FIG. 4, the amount of adsorption decreases as the temperature is raised, so that the adsorption and desorption of acetylene can be performed efficiently by adding the temperature operation to the pressure operation.

  In another embodiment of the porous metal complex according to the present invention, the porous metal complex is formed of a divalent transition metal cation and a first ligand that is a divalent anion having a site capable of coordinating with a metal. It is also conceivable to form a porous structure by linking the layered structure in a columnar shape with the second ligand, and to control the pore diameter by the substituent introduced into the first ligand.

  This porous metal complex uses a zinc salt as a divalent transition metal cation, and 9,10-anthracene as a first ligand which is a divalent anion having a site capable of coordinating with a metal. Dicarboxylic acid or 1-4 naphthalenedicarboxylic acid is used, and the pillar ligand 1,4-diazabicyclo [2,2,2] octane is used as the second ligand and mixed in a dimethylformamide (DMF) solution. To be synthesized. The obtained porous metal complex is obtained by powdering.

  In addition, as this 2nd ligand, it changes into the above-mentioned 1, 4- diazabicyclo [2, 2, 2] octane, and is a compound which has a nitrogen atom in both ends, such as a pyrazine and 4,4'- bipyridyl. Can also be used.

  Furthermore, as the divalent transition metal cation, in addition to the zinc and the above-described copper, a divalent cation state can be taken and a hexacoordinated octahedral coordination structure can be formed. For example, iron, cobalt, manganese, It is also possible to use transition metal elements such as chromium.

  Furthermore, you may introduce | transduce the substituent of a methyl group, a hydroxyl group, and a carboxyl group into the dicarboxylic acid of the 1st ligand for adjusting a pore diameter and adsorption power.

  This porous metal complex has the pore structure shown in FIG. 5, and the adsorption power and adsorption amount of acetylene are improved as compared with the conventional porous metal complex.

(1) 1 g of zinc nitrate hexahydrate, 0.88 g of 9,10-anthracene dicarboxylic acid, and 0.19 g of 1,4-diazabicyclo [2,2,2] octane are mixed with methanol: DMF = Together with 100 mL of the mixed solvent mixed 1: 1, the mixture was accommodated in an eggplant flask and heated to 60 ° C.
(2) The resulting white precipitate is filtered off for 12 hours, washed with methanol, and dried in vacuo.

From the result of the powder X-ray diffraction measurement of the obtained powder, it was confirmed that the structure shown in FIG. 6 was formed.
Further, as a result of X-ray crystal structure analysis of a single crystal obtained separately, the layered structure shown in FIG. 7 has a pore structure connected by 1,4-diazabicyclo [2,2,2] octane as shown in FIG. I confirmed that there was.

(1) In 500 mL of methanol solvent, 0.4 g of copper formate tetrahydrate and 0.53 g of 9,10-anthracene dicarboxylic acid were stirred for 48 hours at room temperature, and the precipitate was separated by filtration.
(2) Put 25 mL of the resulting precipitate into a pressure vessel, and add 6 mL of toluene and 6 mL of methanol and 0.22 g of 1,4-diazabicyclo [2,2,2] octane in the pressure vessel. And heated at 150 ° C. for 12 hours.
(3) The resulting precipitate was filtered off, washed with methanol, and dried in vacuo.

  From the result of the powder X-ray diffraction measurement of the obtained powder, it was confirmed that the structure shown in FIG. 6 was formed.

(1) 0.75 g of zinc nitrate hexahydrate, 0.53 g of 1-4 naphthalenedicarboxylic acid, 0.138 g of 9,10-anthracene dicarboxylic acid in 40 mL of dimethylformamide using a pressure vessel, 120 Heated to ° C.
(2) After heating for 12 hours, the resulting white precipitate was filtered off, washed with methanol, and dried in vacuo.

  From the result of the powder X-ray diffraction measurement of the obtained powder, it was confirmed that the structure shown in FIG. 6 was formed.

(1) In 500 mL of methanol solvent, 0.4 g of copper formate tetrahydrate and 0.43 g of 1-4 naphthalenedicarboxylic acid were stirred at room temperature for 48 hours, and the precipitate was filtered off.
(2) Put 25 mL of the resulting precipitate into a pressure vessel, and add 6 mL of toluene and 6 mL of methanol and 0.22 g of 1,4-diazabicyclo [2,2,2] octane in the pressure vessel. And heated at 150 ° C. for 12 hours.
(3) The resulting precipitate was filtered off, washed with methanol, and dried in vacuo.

  From the result of the powder X-ray diffraction measurement of the obtained powder, it was confirmed that the structure shown in FIG. 6 was formed.

[Comparative Example 4]
(1) In 500 mL of methanol solvent, 0.4 g of copper formate tetrahydrate and 0.33 g of terephthalic acid were stirred for 48 hours at room temperature, and the precipitate was filtered off.
(2) Put 25 mL of the resulting precipitate into a pressure vessel, and add 6 mL of toluene and 6 mL of methanol and 0.22 g of 1,4-diazabicyclo [2,2,2] octane in the pressure vessel. And heated at 150 ° C. for 12 hours.
(3) The resulting precipitate was filtered off, washed with methanol, and dried in vacuo.

From the result of the powder X-ray diffraction measurement of the obtained powder, it was confirmed that the structure shown in FIG. 6 was formed.

The measurement results of the acetylene adsorption amounts at 298 K and near atmospheric pressure in Examples 1 to 5 and Comparative Example 4 are shown in the following table, and the acetylene adsorption isotherm of the porous material is shown in FIG.

As can be seen from this table, the porous metal complex according to the present invention can improve the acetylene adsorption amount by 60 to 100% as compared with the conventional porous metal complex mentioned as Comparative Example 4.
In this case, since the benzene ring introduced into the dicarboxylic acid protrudes into the pores, the pore diameter becomes small. However, when the pore diameter becomes small, the force for adsorbing gas molecules becomes strong and the acetylene adsorption amount increases.

FIG. 10 is a flowchart showing an example of a high-purity acetylene supply device using the above-described porous metal complex.
This high-purity acetylene supply device is composed of a container (2) filled with a porous metal complex (1) having an acetylene adsorption capacity, a heater (3) for heating the container (2), and a flow rate in the container (2). It is comprised with the diamond aram type dry vacuum pump (5) connected in communication via the regulating valve (4).

  In this high-purity acetylene supply device, the container (2) filled with the porous metal complex (1) is evacuated and pretreated, and separately purified high-purity acetylene gas is stored in the container (2). Is adsorbed on the porous metal complex (1) and desorbed by operating the vacuum pump (5) to supply a high-purity acetylene gas containing no solvent vapor.

FIG. 11 is a flowchart showing an example of a high-purity acetylene purification apparatus using a porous metal complex.
This high-purity acetylene refining apparatus shows a case where high-purity acetylene is obtained from dissolved acetylene distributed in the market.
In the figure, reference numeral (6) is a dissolved acetylene container, (7) is a moisture / solvent removal tower packed with an adsorbent such as activated carbon or zeolite, (8) is an acetylene purification tower packed with the porous metal complex according to the present invention, (9) is a vacuum pump for reducing the pressure inside the acetylene purification tower and transferring the adsorbed gas to another tower or exhausting it out of the system. (10) is adsorbed by heating each purification tower (8). It is a heater for desorbing acetylene gas.

In this high-purity acetylene purification apparatus, a pretreatment consisting of removing the solvent vapor or water of acetone or dimethylformamide contained in the dissolved acetylene by a water / solvent removal tower (7) is performed, and this pretreated acetylene is removed from the acetylene. It introduce | transduces into a purification tower (8).
In the acetylene purification tower (8), by using the property that the porous metal complex absorbs and desorbs acetylene, the acetylene purification tower (8) can be purified using a pressure swing method or a temperature swing method to obtain a high-purity acetylene gas. In this case, the pressure swing method is an operation in which the raw material gas is adsorbed in the acetylene purification tower (8) from which the adsorbed gas has been desorbed in advance, and is transferred to another tower and re-adsorbed by the operation of the self-pressure or vacuum pump. Is repeated, and impurities are removed by repeating re-adsorption-desorption to obtain purified acetylene gas. On the other hand, in the case of the temperature swing method, the adsorbed gas is desorbed by heating, the pressure is increased, the gas is transferred to another tower, and re-adsorption-desorption is repeated to remove impurities and obtain purified acetylene gas.
In order to improve the efficiency of the purification process, the two may be combined to constitute an apparatus.

It is a graph which shows the result of a thermogravimetric analysis. It is a graph which shows the relationship between the pressure and adsorption amount of each complex. It is a graph which shows the nitrogen gas adsorption amount in liquefied nitrogen temperature. It is a graph which shows the relationship between adsorption amount and temperature. It is a figure which shows the pore structure of a porous metal complex. It is a figure which shows the structure of the produced | generated powder identified by the powder X-ray-diffraction measurement. It is a figure which shows the structure of a single crystal. FIG. 8 is a diagram showing that the layered structure shown in FIG. 7 is a pore structure connected by 1,4-diazabicyclo [2,2,2] octane. It is a graph which shows the acetylene adsorption isotherm of a porous substance. It is a flowchart which shows an example of a high purity acetylene supply apparatus. It is a flowchart which shows an example of a high purity acetylene refinement | purification apparatus.

Claims (12)

  A first ligand that is a divalent transition metal cation, a divalent anion having a site capable of coordinating to a metal, and a second coordination having sites capable of coordinating to a metal at both ends. An acetylene occlusion material comprising a porous metal complex having pores suitable for acetylene adsorption composed of a child.   No charge having a divalent transition metal cation, a first ligand that is a divalent anion having a site capable of coordinating to a metal, and a site having a site capable of coordinating to a metal at both ends. The acetylene storage material of Claim 1 comprised with a 2nd ligand.   The acetylene occlusion material according to claim 1 or 2, wherein the molar ratio of the transition metal cation constituting the porous metal complex to the first ligand and the second ligand is 2: 2: 1.   The second ligand links the layered structure formed by a divalent transition metal cation and a first ligand that is a divalent anion having a site capable of coordinating with a metal in a columnar shape. The acetylene occlusion material according to claim 1, wherein a porous structure is formed by controlling the pore diameter by a substituent introduced into the first ligand. A layered structure formed by a divalent transition metal cation and a first ligand selected from a 1,4-naphthalenedicarboxylic acid derivative and a 9,10-anthracene dicarboxylic acid derivative is arranged on the metal at both ends. A porous structure is formed by connecting the second ligand having a site capable of positional binding in a columnar shape, and the pore diameter is controlled by a substituent introduced into the first ligand.
Chemical formula: [M ₂ (L1) ₂ (L2)] _n
The acetylene storage material of Claim 1 or 5 represented by these.
(M is a divalent transition metal cation, L1 is the first ligand, L2 is the second ligand)   6. The first ligand is 9,10-anthracene dicarboxylate ion, the second ligand is 1,4-diazabicyclo [2,2,2] octane, and the metal is either copper or zinc. The acetylene storage material described.   The first ligand is 1,4-naphthalenedicarboxylate ion, the second ligand is 1,4-diazabicyclo [2,2,2] octane, and the metal is either copper or zinc. The acetylene storage material described. A first ligand obtained by neutralizing a divalent transition metal cation, at least one selected from 2,3-pyridinedicarboxylic acid and 2,3-pyrazinedicarboxylic acid, and represented by the following structural formula: The chemical formula obtained by mixing and reacting the second ligand, which is a pyridine derivative, in a molar ratio of 2: 2: 1 in water or a mixed solvent of water and methanol or ethanol: [M ₂ (pdc) ₂ (ap)] _n
The acetylene storage material of Claim 1 represented by these.
(M is a divalent transition metal cation, pdc is a 2,3-pyridinedicarboxylate ion or 2,3-pyrazinedicarboxylate ion, ap is a pyridine derivative, n = 1 to 3)

Mixing and reacting a cupric salt, a salt obtained by neutralizing 2,3-pyrazinedicarboxylic acid, and 4-aminomethylpyridine in water at a molar ratio of 2: 2: 1. The chemical formula: [Cu ₂ (pzdc) ₂ (4-amp)] _n
The acetylene storage material of Claim 1 represented by these.
(Pzdc is 2,3-pyrazinedicarboxylate ion, 4-amp is 4-aminomethylpyridine)   The acetylene storage container which stores the acetylene which filled the acetylene storage material of any one of Claims 1-9 inside.   A high-purity acetylene gas supply device comprising: an acetylene storage container filled with the acetylene storage material according to any one of claims 1 to 9; and a pressure operating mechanism for depressurizing the container to desorb acetylene gas. .   An apparatus for purifying high-purity acetylene comprising a tower packed with the acetylene storage material according to any one of claims 1 to 9 as an adsorption separation material, and at least one of a pressure operation mechanism and a temperature operation mechanism.

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